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Structure and properties of radical anion and dianion salts of organic dye trans-perinone and mixed salt of gallium(III) phthalocyanine and trans-perinone radical anions {cryptand(K+)}[(perinone)0.5(Ga(III)ClPc)](-)·3C6H4Cl2статья
- Авторы: Faraonov Maxim A., Romanenko Nikita R., Mikhailenko Maxim V., Kuzmin Alexey V., Khasanov Salavat S., Konarev Dmitri V.
- Журнал: New Journal of Chemistry
- Том: 45
- Номер: 30
- Год издания: 2021
- Издательство: Royal Society of Chemistry
- Местоположение издательства: United Kingdom
- Первая страница: 13599
- Последняя страница: 13607
- DOI: 10.1039/d1nj01636a
- Аннотация: Reduction of organic dye trans-perinone (its abbreviation is perinone) in different experimental conditions allows us to obtain and characterize radical anion {cryptand(K+)}[perinone(2-)] (1) and dianion {PPN+}2[perinone(2-)].2C6H4Cl2 (2) salts of this dye. The salts have layered structures. Perinone(.-) radical anions form pi–pi stacked dimers in 1 with an effective interaction between them, whereas perinone2 dianions are isolated in 2. Reduction of perinone is accompanied by an essential red shift of the absorption bands of the starting dye and, as a result, the salts have absorption nearly in the whole visible range. Strong coupling of spins is observed in the p-stacking [perinone(2-)]2 dimers of 1, which are described by the Heisenberg model for isolated pairs of antiferromagnetically interacting spins with J/kB = -38 K. The triplet excited state of the dimers is populated above 50 K. The EPR signal of 1 shows features characteristic of triplets, and the average separation of spins within the dimers estimated in the point-dipole approximation is 8.7 Å. The dimers manifest an intense charge transfer band with a maximum at 1356 nm. A mixed {cryptand(K+)}[(perinone)0.5(Ga(III)ClPc)](.-).3C6H4Cl2 (3) salt with two anionic chromophores – perinone and gallium chloride phthalocyanine – is also obtained in the crystalline form. It has only one negative charge and spin per [(perinone)0.5(Ga(III)ClPc)] unit. As a result, the magnetic behavior of 3 is described well by contributions from isolated perinone radical anions and {Ga(III)ClPc}2(.-) dimers with effective pi–pi stacking between phthalocyanines and one negative charge and S = 1/2 spin per dimer.
- Добавил в систему: Конарев Дмитрий Валентинович